The Advanced Hyperspectral Imager (AHSI), carried by the Gaofen-5 (GF-5) satellite, is the first hyperspectral sensor that simultaneously offers broad coverage and a broad spectrum. Meanwhile, deep-learning-based approaches are emerging to manage the growing volume of data produced by satellites. However, the application potential of GF-5 AHSI imagery in lithological mapping using deep-learning-based methods is currently unknown. This paper assessed GF-5 AHSI imagery for lithological mapping in comparison with Shortwave Infrared Airborne Spectrographic Imager (SASI) data. A multi-scale 3D deep convolutional neural network (M3D-DCNN), a hybrid spectral CNN (HybridSN), and a spectral–spatial unified network (SSUN) were selected to verify the applicability and stability of deep-learning-based methods through comparison with support vector machine (SVM) based on six datasets constructed by GF-5 AHSI, Sentinel-2A, and SASI imagery. The results show that all methods produce classification results with accuracy greater than 90% on all datasets, and M3D-DCNN is both more accurate and more stable. It can produce especially encouraging results by just using the short-wave infrared wavelength subset (SWIR bands) of GF-5 AHSI data. Accordingly, GF-5 AHSI imagery could provide impressive results and its SWIR bands have a high signal-to-noise ratio (SNR), which meets the requirements of large-scale and large-area lithological mapping. And M3D-DCNN method is recommended for use in lithological mapping based on GF-5 AHSI hyperspectral data.